Process of steam fractionation



Maylz, 1942.

J. E. JEWETT PROCESS OF STEAM FRACTIONATION Filed May 2e, 1959.

FIG. v2.

5 Shets-Sheet 2 INVENTOR.

' BY Masha/af i afa/f77',

ATTORNEY.

May 12 1942 J. E. JEwE'r-r 2,282,982

PROCESS OF STEAM FRACTIONATION Filed May 26. 1959 3 Sheets-Shea?l 3 WATER our WATER i- Pioacr 23 BY www ATTORNEY.

A pressure and substantial Patented May 1.2,A 1942 PROCESS F STEAM FRACTIONATION Joseph E. Jewett, Larchmont, N. Y., assignor to American Cyanamid and Chemical Corporation, New York, N. Y., a corporation oi' Del- Application May 2c, 1939, serial No. 275,804

(ci: 2oz-12) l Claim.

distillation however introduces the riskof attack on the terpenes during fractionation by air drawn into a fractionating column which is not air-tight.- For example, it has been observed that air entering the fractionating lcolumn in the vacuum fractionation o! sulfate turpentine for thev separation of alpha-pinene, beta-pinene and dipentene therefrom, causes formation oi insoluble resins therein which rapidly accumulate and cause stoppages in the' vapor passages of the fractionating column. A further disadvantage in the vacuum fractionation ofterpenes lies in the risk of oxidizing by air, which has leaked into the column, oxidizable terpenes such as alphaand beta-pinche, dlpentene, terpinolene and alphaand beta-terpinene.

My invention therefore has as an object' a process for the fractional separation of terpenes and similar compounds which are subject to attack by vair under fractionating conditions, whereby leakage of air into the fractionating column during distillation may be,avoided and reduced fractionating temperatures obtained.

This object of my invention may be accomplished by .conducting the fractionation of the terpenes in an atmosphere of steam at a pressure in the fractionating column at least equal .to that of the surrounding atmosphere. In this way. due tothe absence of a pressure diierence, air cannot leak into the fractionatlng column.

While the invention may be best practiced by using a pressure in the fractionating column which is at least equal to the pressure of the surrounding atmosphere, the column may 'be operated at a pressure slightly below atmospheric applicable, for

prevention of air-leak- `materials may be transferred' tothe sulfate turpentine, a by-product recovered from the blow-oi! gases o fv the digester in the sulfate process for pulping pine wood. a heads cut containing organic sulfur compounds is first distilled oil and then the 'alpha-pinene cut distilled, whereby there is left in the still, a. crude residue such as described above. This crude res- Aidue is not uniform in character and its constitution will vary according to the constituents of the crude sulfate turpentine and the extent of the removal of the alpha-plnene therefrom.

The invention may be used to separate other terpenes which are subject to attack by air under fractionating conditions where the partial pressures'of the terpenes in an atmosphere of steam are of sulciently diilerent magnitudes to allow of their separation therein.

'Ihe second part of my invention has for its object the conservation of heat in a reduced temperature iractionating system.

In order to accomplish this object of my invention I have designed processes and apparatus whereby latent heat of vaporization given up in the condensation of eiiluent vapors from the steam fractionation of water-immisclble organic contents of the still.

The operation. 'of certain of these processes and apparatus is based on the principle thatV by compression of a vapor its temperature orl heat level may be raised. In these vapor compression heating processes and apparatus of my invention, either the eiiluent 'vapors from the fractionating column of a steam fractionating process operated with a pressure in the column not below atmospheric pressure, or a secondary vvapor generated by condensing `these eilluent vapors by indirect heat exchangewith a vaporizable liquid, may be compressed to' the degree necessary to elevate the condensing temperature thereof above the temperature of the contents of the still. VThe compressed vapor when brought into indirect heat exchange with 'the contents of the still will be condensed and the contents of the still heated by latentheat or vaporization given up by its condensation. j

Vapor compression heating of the contents o! the still of a normal boiling point or of a vac-- uum tractionatins systemV is impracticable because of the largeV temperature diiferential between the vapors in the fractionating column :top and the charge in the still. but with steam fractionation this temperature diirerentialis re- While this aspect of my invention is applicable to the fractionation of all water-immisclble organic materials it is particularly well suited to the fractionation of terpenes which are subject to attack by air under fractionating conditions since steam fractionation allows of the provision in the fractionating column of a pressure sufficient to prevent air leakage thereinto.

In the accompanying drawings are shown in diagrammatic form several modications of apparatus designed, in accordance with my invention, for the carrying out of the several processes of this part of my invention, and in which:

Fig. 1 thereof is an apparatus designed for compression of the effluent vapors of the fractionating column and for bringing the compressed vapor into indirect heat exchange with the contents 'of-the still;

Fig. 2 thereof is a modified design of apparatus for the generation of a secondary vapor from the heat of the eilluent fractionating columnvapors, compression of the secondary vapor, and for bringing the compressed secondary vapor into indirect heat exchange with the contents of the Still; and

Fig. 3 thereof is a modified design of apparatus separator I3 for separation of the liquids therein by decantation. If the condensate be too hot for practical separation in the liquid separator itmay be cooled by some suitable cooling means before it is introduced therein. Water is decanted from the separator through pipe Il and returned to the still through connecting pipe I5. 'I'he distillate is withdrawn by pipe I6 and delivered by pipe Il to branch pipes I8 and I9, connected for delivery of the distillate to flow meters such as Rotameters and 2| respectively. The iiow meters measure the amount of distillate constituting reflux and product respectively. Branch pipe I8 is provided with a valve 22 which controls the amount of distillate taken out of the system as product through pipe 23. That part of the distillate not removed as product is passed through line I8, ilow meter 20 and feed line 24 to the top of the fractionating column to serve as reflux for the generation of steam as secondary vapor and 'delivery of the steam into the still.

Referring to Fig. 1 the construction and operation of the apparatus shown therein for carrying out of one form of process is as follows. The Water-immiscible organic material to be fractionally distilled, which may be the crude still residue described above, is fed along with a supply of water to the still I by am suitable means and the mixture therein heated to produce steam and components of the vapors to be fractionated, the mixed vapors passing through pipe 2 to the fractionating column 3 where they undergo the fractional separation in an atmosphere of steam. The fractionating column is sectional and of the bubble cap type, andlagged against heat loss therefrom. The eilluent vapors leaving the fractionating column pass through the vapor line 4 to a vapor compressor 5 of any suitable construction, where they are compressed and their temperature raised to a point such that upon being brought into indirect heat' exchange with the relatively cooler contents of the still they will be condensed. For example, if the temperature of the still contents is 105 C., which at this point vmay be mentioned as a suitable temperature for the fractional distillation of the crude still residue, then the eiiluent vapors may be compressed to produce a vapor temperature of about 11o-115 C. which is sufficiently high to produce the necessary heat head between the compressed vapor and the liquid contents of the still to cause transfer of heat therebetween and condensation of the vapor.v The compressed vapor -is then brought into indirect heat exchange in heat exchanger 8 with the relatively cooler liquid charge of the still delivered to the heat exchanger by means of a pump 1 and feed line l. The compressed vapor having a temperature high enough to allow of its condensation by thecooler contents of the still is condensed in the heat exchanger and in the condensation gives up latent heat of vaporization to the liquid charge which is returned to the still through the pipe I. The condensate in the heat exchanger is removed through pipe Il to a pump l l, which will supply any force necessary in addition to the pressure on the condensate to elevate the condensate through line I2 to a liquid therein. Condensate from the'fractionating column is. returned to the still through pipe 25. 'I'he water losses of the system can be made up by injection of steam through pipe 26 into the con# tents of the'still passing through return pipe l.

To start up 'the fractionating apparatus the mixture of water and material to be distilled is circulated from the still by pump 1 and pipes 8 and 9 through the heat exchanger 6 to which steam is supplied by supply line 21, a check valve 28 in the vapor line operating to prevent passage of steam therethrough.

Referring to Fig. 2, this design of apparatus is for the carrying out of a modification of the above described process of heat recovery in a steam fractionation of water-immiscible organic materials where the nature of the eiiluent vapors from the fractionating column makes their passage through a compressor inadvisable. 'Ihe construction and Voperation of this modified design ofl apparatus is as follows: The e'nluent vapors from the fractionating column' 3. are brought into heat exchange with a vaporizable liquid in a boiler condenser |00, which is of the type wherein the heating medium, and in this case the hotemuent vapors from the fractionating' column, pass around tubes containing the vaporizable liquid.'

The eiliuent vapors from the fractionating column as they pass around the tubes will be'condensed by heat exchange with the vaporizable llquidtherein and in condensing will give up latent` heatof vaporization thereto, generating a vapor therefrom which will be termed secondary' vapor. Where water is usedin the tubes of the boiler condenser, as the vaporizable liquid. the secondary vapor will of course be steam. For convenience in description,- the vaporizable liquid will be referred to in terms of water, and accordingly, the secondary vapor in terms of steam, although it will be understood that any suitable vaporizable liquid may be used in the boiler condenser in place of water. The steam generated in the boiler condenser ispassed through a pipe Illl to a steam-water separatori, the water which separates out returning through a pipe lll to the tubes ofthe boiler condenser. The steam from the separator "2 is passed through a pipe I to the vapor compressor l where it is com-` pressed to raise its temperature to a sumciently high level that, upon being brought into heat ex change with the cooler contents of the still, it

h will be condensed thereby and latent heat of vaporization will be released for transfer to the contents of the still. which are circulated through is passed through a pipe |05 to a pump |06 which will supply any force necessary, in addition to the pressure on the condensate, to elevate the Water through a pipe .|01 to the tubes of the boiler condenser. The eiliuent vapors are passed as condensate from the boiler condenser throug pipe |08 to the liquid separator I3.

In case the temperature ofthe eluent vapors from the fractionating column is below the normal boiling point of the Water'in the boiler condenser there Will be, of course, no generation of steam for delivery to the Avapor compressor. This unbalance in the system "will however be adjusted by the action of they vapor compressor, which, when no steam or an insufcient amount thereof is fed thereto, will act as an exhauster on the water tubes in the boiler condenser and produce a partial vacuum therein, lowering the boiling point of the water to a'` value suiciently low to cause generation of steam therefrom. In order to avoid in thiscas'e, a vacuum in the fractionating column due tothe condensation of the eiliuent vapors in the boiler condenser at the time when no, or an insuicient amount of vapor is being fed to the vapor compressor, which action would result; in a heat deficiency in the still because of no heat recovery, steam may be injected into the heat' exchanger 6 through a line 21 whereby heat is added to the still and the distillation rate increased. By increasing the rate of vapor generation in the still, the pressure in the column may be kept up to 'atmospheric pressure bythe addition ,of the vapors fed thereto. ,The apparatus otherwise is operated in the manner described for the corresponding apparatus parts of Fig. 1.

Referring to Fig. 3, this design of apparatus is for 'the carrying out of a mod ied heat recovery process in a steam fractionation of materials. The construction and operation of this design of apparatus is as follows:

The eilluent vapors from the fractionating co1- umn are passed around the water containing tubes of the boiler condenser /I00, where in heat exchange with the water they are condensed, the condensate therefrom being lpassed to the separator I3, and the steam generated in the boiler condenser, after having passed through the steam-water separator I 02, is compressed by a vapor compressor 200 to a pressure high enough the same as previously l 3 to overcome the back pressure .on the still I, the steam under this pressurepassing into the still through a pipe 203|,

lwhich is perforated for admission of the steam into the contents of the still. The water from the liquid separator I3 instead ofbeing returned to the still may be either removed from the system by a line 202, in which case fresh "water'will be supplied to the boiler condenser, or may be sent in required amounts through aline 203 to the water tubes of the boiler condenser.

vTo start Yup, this form of apparatus steam is injected through suiiicient volume of vapors are supplied from the fractionating tower 3 condenser vent steam from passing into the vapor line. This pipe 26 will also serve to supply steam for making up heat and water losses in the system. The operation, otherwise, of this design of apparatus is sponding apparatus parts in Figs. 1 and 2.

By operating the steam fractionation in accordance with any of the above procedures the amount of extraneous heat to be added to the fractionating 'system is limited to substantially the amountof heat loss therefrom. In some cases in' the vapor compression heating 'processes the work done on the vapor by the compressor Imay make up all the heat loss "from the system.

The above described embodiments of thel several parts of my invention are given by way'of illustration and not by way of limitation thereof except as included in the appended claim.

What I claim is: *Y

v'I'he process o f fractionally `disti11ing Waterimmiscible organic materials which comprises, generating steam and vapors of the components to be distilled from a. mixture of vwater and a water-immiscible organic material contained in a still, fractionating said components vin said steam, condensing the eiuent. vapors from th fractionation by indirect heat exchange with a vaporizable liquid thereby generating a vapor from the latter, compressing this vapor, and, condensing it and transferring latent heat of vaporization therefrom to the contents of the still by passing the compressed vapor in heat exchange with the latter.

- JOSEPH E. JEWEIT.

-the terminal portion of pipe 26 into the still until a through pipe 4 to the boiler |00, check valve 28 operating to predescribed for, the corre- 

